Hair set lacquer and lotion composition

ABSTRACT

Hair lacquer and lotion compositions containing in a cosmetically acceptable vehicle or carrier a copolymer of 40-90 weight percent N-vinyl pyrrolidone, 5-40 weight percent vinyl ester and 3-20 weight percent unsaturated monobasic carboxylic acid.

United States Patent [191 Viout et a1.

[ June 18, 1974 HAIR SET LACQUER AND LOTION COMPOSITION [75 Inventors: Andre Viout, Paris; Christos Papantoniou, Epinay-sur-Seine, both of France [73] Assignee: Societe Anonyme diti LOreal, Paris,

France [22] Filed: Mar. 2, 1973 21] Appl. No.: 337,467

Related U.S. Application Data [62] Division of Ser. No. 34,580, May 4, 1970, Pat. No.

30 Foreign Application Priority Data May 9, 1969 Luxembourg 58617 [52] U.S. Cl. 260/8012, 8/l27.5l, 260/29.6 TA,

260/326 R, 260/334 R,424/DIG. 1, 424/D1G. 2, 424/71, 424/78 3,405,084 10/1968 Bohac et a1 260/29.6

1 Primary Examiner-Stanford M. Levin Attorney, Agent, or Firm-Cushman, Darby &

Cushman v [571 ABSTRACT.

Hair lacquer and lotion compositions containing in a cosmetically acceptable vehicle or carrier acopolymer of 40-90 weight percent N-vinyl pyrrolidone, 5-40 weight percent vinyl ester and 3-20 weight percent unsaturated monobasic carboxylic acid.

1 Claim, No Drawings 1 HAIR SET LACQUER AND LOTION COMPOSITION This is a division of application Ser. No. 34,580 filed May 4, 1970, now US. Pat. No. 3,743,7l5.

This invention relates to a novel hair set lacquer and lotion composition and to novel copolymers useful in the preparation of hair set lacquers and lotions. More particularly, the present invention relates to a hair set lacquer or lotion composition which contains a copolymer of N-vinyl pyrrolidone with at least one vinyl ester and at least one monobasic unsaturated acidcontaining 4-1 1 carbon atoms. The invention also relates, specifically to novel copolymers of N-vinyl pyrrolidone with one of vinyl stearate or vinyl laurate and with a monobasic unsaturated acid selected from the group consisting of crotonic, vinyl acetic, allylacetic or allyloxyacetic acid.

Heretofore hair set lacquers and lotions have been produced using as the principal lacquering or setting ingredient a' copolymer of N-vinyl pyrrolidone with acrylic acid and an acrylate. Still other prior-art hair set lacquers and lotions have been formulated with a terpolymer of N-vinyl pyrrolidone, vinyl stearate and either vinyl acetate or acrylic ester. lt has also been known to employ in conventional hair set lotions and lacquers a copolymer of N-vinyl pyrrolidone and vinyl acetate as well as a copolymer obtained by copolymerizing 80 to 95% N-vinyl-e-caprolactam with a vinyl ester, a methacrylate, an acrylate, an acrylamideor a vinyl ether.

While such polymers have been found to be advantageous over shellac based hair set lacquers and lotions which they replaced,.such polymer based compositions exhibit certain disadvantages in that they do not possess to the degree desired such characteristics as solubility in water and in alcohols, for instance, lower alkanols, film strength sufficient to control hair placement and film resiliency or plasticity to permit the hair to be combed without undue breakage of the film. Further, such pfior art hair set lacquers and lotions were often difficult to remove from the hair and extensive build-up fected in the presence of a catalyst such as benzoyl peroxide, lauroyl peroxide or azobis-isobutyronitrile, the

catalyst being present in the reaction mass in amounts ranging from about 05-5 and, preferably, about 0.9-3 weight percent of the weight of the starting monomers.

chain is interrupted by an oxygen atom. Particularly useful acids are crotonic acid, allyloxyacetic acid,

allyloxypropionic acid, vinyl acetic acid, allylacetic acid and vinyloxyacetic acid. A

Further, the film-forming copolymers thus produced from monomeric monobasic unsaturated acids can be neutralized by reacting'the copolymer with an inorof residual film on the hair resulted in an undesirable appearance characteristic.

It has now been found that the disadvantages'of prior art hair set lacquers and lotions can be overcome by the present invention wherein the novel hair set lacquer and lotion possesses significantly improved water and- /or alcohol solubility properties, even when the canboxyl substituents on the polyrner chain are not neutralized. Further, the film produced by the hair set lacquer or lotion exhibits highly improved plasticity characteristics and said film or resin can be more easily and completely removed, when desired, by simple techniques such as brushing or shampooing the hair.

Thus, the novel hair set lacquer and lotion composition of this invention comprises a cosmetic vehicle and a film-fonning copolymer of 40-90 weight percent N- vinyl pyrrolidone, 5-40 weight percent of at leastone vinyl ester and 3-20 weight percent of at least one monobasic unsaturated acid containing 4-Il carbon the solvent can be, for example, an alcohol, a glycol or a glycol ether. The polymerization is preferably efganic or organic base using conventionaltechniques. The degree of neutralization can range between-about 50 to 150% of the level corresponding tostoichiometric neutralization.

Among the mineral and organic bases that can be utilized are, for instance, ammonia, 1,3 amino-Z-methyl- 2-propanediol (AMPD), 1,3 amino-2-ethyl-2- propanediol (AEPD), triethanolamine (TEA) and the like. The neutralization reaction can take place at atmospheric pressure in the presence of asolvent for the copolymer, if desired, such as an alcohol, for instance ethyl alcohol or the like.

Generally, the molecular weight of the copolymers used in, the film-forming compositions of the invention ranges between about 10,000 and 100,000.

The cosmetic vehicle or carrier employed in combinationwith the film-forming copolymer to produce the hair set lacquer and lotion of this invention can be any conventional cosmetically acceptable vehicle or carrier such as alcohol, preferably a lower alkanol, water and their mixtures. Additionally, the hair set lacquer and lotion canbe produced in the form of a solution, a gel, a cream or a foam and ideally it can be provided in the form of a sprayable aerosol composition.

For instance, in accordance with the present invention, an aerosol lacquer for the hair can be made by introducing l to 4 weight percent of a copolymer such as those described above into a mixture comprising onefourth to one-third by weight alcohol, such as ethyl alcohol or any other-.convenient lower alkanol,and twothirds to three-fourths by weight pressurized liquid proless than alcohol. Preferably the alcohol is a lower alkanol.

The cosmetic compositions of the invention can also include cosmetic adjuvants of the usual kind such as plasticizers, perfumes, dyes, cationic products to facilitate untangling, nonionic products to ensure peptizing ,of the perfumes, silicones to enhance brilliance, or

other cosmetic resins.

The present invention is also directed to novel copolymers of 40-90 weight percent N-vinyl pyrrolidone, 5 to 40 weight percent of a comonomer selected from the group consisting of vinyl stearate and vinyl laurate and 5-20 weight percent of a further comonomer selected from the group consisting of crotonic acid, vinyl acetic acid, allylacetic acid and allyloxyacetic acid. The novel copolymers can be produced by employing conventional polymerization techniques as described hereinbefore.

In the following examples, which further illustrate the present invention, all parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 Preparation of a N-vinyl pyrrolidone (75%)lvinyl stearate (l5%)/allyloxyacetic acid copolymer In a 250 ml vessel fitted with an agitator, a reflux cooler, a thermometer and nitrogen lead-in tube, there are placed75 g N-vinyl pyrrolidone, g vinyl stearate, 10 g allyloxyacetic acid, 200 g ethanol and 0.7 g azobis-iso-butyronitrile. The mixture is heated to 78 to 82C. with reflux for l6 hours.

After cooling, there is obtained in quantitative yield a very'pale amber viscous product. Precipitation of the copolymer is effected with petroleum ether and after drying the desired copolymer is obtained in a 75% yield, having the following characteristics:

Acid Number: 39.] (calculated value: 48)

Viscosity 2.0 cp (51 copolymer solution in DMF at 35C) EXAMPLE 2 Preparation of N-vinyl pyrrolidone (70%)lvinyl laurate (%)/allyloxyacetic acid (10%) copolymer In a 250 ml vessel fitted with an agitator, a reflux cooler, a thermometer and a nitrogen lead-in tube, there are placed 70 g N-vinyl pyrrolidone, 20 g vinyl laurate, 10 g allyloxyacetic acid, 200 g ethanol and l g azo-bis-iso-butyronitrile. The mixture is heated to 80C. and held at this temperature for 10 hours.

After cooling, there is obtained in quantitative yield, a viscous product. The desired copolymer is then precipitated by the addition of petroleum ether to the cooled reaction mixture and after drying the precipitate the desired copolymer is obtained in a 70% yield. The resulting copolymer has the following characteristics:

Acid number: 46.5 (calculated value: 48)

L68 cp. (5% solution of the copolymer Viscosity in DMF at C.)

EXAMPLE 3 stearate, 20 g crotonic acid, 100 g absolute ethanol and 2 g azo-bis-iso-butyronitrile.

I Viscosity The mixture is heated at a temperature of 80C. with reflux for 24 hours. The reaction mixture is then al- Acid number: I33 (calculated value 130) 1.23 cp (5% solution of copolymer in DMF at 35C.)

EXAMPLE 4" Preparation of N-vinyl pyrrolidone (%)lvinyl laurate (20%)/vinylacetic acid (5) copolymer In a 250 ml vessel fitted with an agitator, a reflux cooler, a thermometer and a nitrogen lead-in tube there are placed 75 g N-vinyl pyrrolidone, 20 g 'vinyl laurate, 5 g vinylacetic acid, 100 g ethanol and 2 g azobis-iso-butyronitrile.

The mixture is heated at a temperature of C. with reflux for 24 hours and then allowed to cool. The resulting copolymer is precipitated by the addition of petroleum ether to the cooled reaction mixture.

The resulting precipitate is dried, and the desired copolymer is obtained as a yellowish powder in a 45% yield, the said copolymer having the following characteristics:

Acid number: 17.32 (calculated value: 32.5)

1.78 cp (5% solution of copolymer in EXAMPLE 5 Preparation of N-vinyl pyrrolidone (%)/vinyl stearate (5)/allylacetic acid (5%) copolymer In a 250 ml vessel fitted with an agitator, a reflux cooler, a thermometer and nitrogen lead-in tube, there are placed 90 g N-vinyl pyrrolidone, 5 g vinyl stearate, 5 g allylacetic acid, g ethanol and 2 g azo-bis-isobutyronitrile.

The mixture is heated at a temperature of 80C. with reflux for 24 hours and then allowed to cool. The re-. sulting copolymer is then precipitated by adding petroleum ether to the cooled reaction mixture.

The precipitate is dried and the desired copolymer is obtained as a white powder in a 30% yield, the said copolymer having the following characteristics:

Acid numbcr: l2.l3 (calculated value: 28)

2.l9 cp (5% solution of copolymer in DMF at 35C.)

weight percent of said vinyl ester. The amount of N- Ethyl alcohol in sufficient quantity vinyl pyrrolidone present in these copolymers ranged from about 40-90 weight percent. Additionally, these copolymers are also produced using additionally acids other than those specified in Examples 1-5 such as allyloxypropionic acid and vinyloxyacetic acid, the acid being present in the copolymers in amounts rangingfrom about 3-20 weight percent.

' Neutralization of such copolymers is also effected by reaction thereof with such alkaline agents as 1,3- amino-2-methyl-2-propanediol, triethanolamine and 1 ,3-amino2-ethyl-2-propanediol.

The following examples illustrate the production, according to the present invention, of hair' lacquers and lotions. 1

g EXAMPLE 6' g The followingsolution is prepared:

Copolymer described in Example I 3 g I.3-amino-2 methyl-2 propanediol in" sufficient quantity for I% neutralization to make 50 Water in sufficient quantity to make up I00 ml This solution is applied to the hair for a wave set and a plastic, very brilliant film is obtained which imparts excellent qualities to the hair set.

EXAMPLE 7 The following solution is prepared:

Copolymer described in Example 2 3 l.3-amino-2 methyl-2 propanediol in sul'ficient quantity for I00; neutralization Ethyl alcohol'in sufficient quantity to make 50 Water in sufficient quantity to make up I00 ml This solution, used hair set lotion, produces a very brilliant plastic film. V

" EXAMPLE 8 To make an aerosol lacquer for the hair, a solution of the following composition is made:

Copolymer described in Example I 7.2 g

Triethanolamine in sufficient quantity for I00; neutralization Perfume 0.3 g

Absolute ethanol in sufficient quantity to make up I00 g Twenty-five g of this solution is, stored in an aerosol can with 47 g of trichloromonofluoromethane and 28 g of dichlorodifluoromethane.

By spraying, a lacquer is obtained that imparts suppleness and great brilliance to thehair.

EXAMPLE 9- To make an aerosol lacquer for the hair, a solution having the following composition is prepared:

Twenty-five g of this solution is stored in an aerosol can with 47 g of trichlorornonofiuoromethane and 28 g of dichlorodifluoromethane.

After spraying, a lacquer is obtainedmthatimparts suppleness and great brilliance to the hair and is easily removed, when desired, by brushing the hair.

EXAMPLE 10 The following solution is prepared:

Copolymer described in Example 3 v 3 g l,3 amino-2 methyl-2 propanediol in sufficient quantity for I00% neutralizatio n Ethyl alcohol in sufficient quantity to make 50% Water in sufficient quantity. to make up I00 When applied as a waveset lotion this solution gives a very brilliant plastic film for the hair.

EXAMPLE II To make an aerosol lacquer for the haira solution having the following composition is prepared:

Copolymerdescribcd in Example 4 Triethanolamine in sufficient quantity. for I00% neutralization Perfume 0.3 g

lsopropyl alcohol in sufficient quantity to make up I00 g Twenty-five g of thissolution is stored in an'aerosol can with 47 g oftrichlorornonofluoromethane and 28- V g of dichlorodifluoromethane.

After spraying there isobtained a lacquer that imparts great brilliance to the hair and out.

EXAMPLE I2 To make an aerosol lacquer for the hair, a solution having the following composition is prepared:

Copolymer described in Example 5 I.3-amino-2 ethyl-2 propancdiol in sufficient quantity for l00% neutralization Perfume 0.3 g

lsopropyl alcohol in sutficient quantity to make up g Twenty-five g of this solution is'stored in anaerosol can with 47g of trichloromonofluoromethane' and 28 g of dichlorodifluoromethane. I

is easily brushed After spraying there is obtained a lacquer thatimparts great brilliance to the hair and is easily removed by brushing or shampooing the hair.

v EXAMPLE 13 The following'solution islprepared:

Copolymer described in Example 4 3 g I l,3-amino-2 m'ethyl-2 propanediol in sufficient quantity for 100% neutralization Ethyl alcohol in sufficient quantity tomake 50 Water in sufficient quantity to make up l00 ml Applied as hair set lotion, this solution gives a plastic film of great brilliance.

, EXAMPLE 14 The following solution is prepared:

CopoIymer described in Example 3 g l.3-amino-2 methyl-2 propanediol in sufficient quantity for 100% neutralization Ethyl alcohol in sufficient quantity to make 50 Water in suflicient quantity to make up I00 ml I When applied as a hair set lotion, this solution gives I vinyl propionate, vinyl butyrate, vinyl caproate, vinyl" octanoate, vinyl palmitate and vinyl behenate and (3) acids also other than those of Examples [-5 herein, for

instance, allyloxypropionic acid and 'vinyloxyacetic acid.

Moreover solutions useful ashair set lotions are also prepared in amanner essentially as that set forth in Examples 6, 7, l0, l3 and 14 using the same additional vinyl esters and acids disclosed immediately above,

which esters and acids are in addition to those specifically recited in Examples l-5 herein.

What is claimed is:

l. A film-forming copolymer having a molecular weight ranging between about 10,000 and 100,000 of to 90 weight percent N-vinyl pyrrolidone, 540 Weight percent of a comonomer selected from the group consisting of vinyl stearate and vinyl laurate and 5-20 weight percent of a further comonomer selected from the group consisting of crotonic acid, vinylacetic acid, allylacetic acid and allyloxyacetic acid.

III F t I 

